Queen Victoria and her husband, Prince Albert, were already concerned with finding a bride for their son and heir, Albert Edward, the Prince of Wales. They enlisted the aid of their daughter, Crown Princess Victoria of Prussia, in seeking a suitable candidate. Alexandra was not their first choice, since the Danes were at loggerheads with the Prussians over the Schleswig-Holstein Question and most of the British royal family's relations were German. Eventually, after rejecting other possibilities, they settled on her as "the only one to be chosen".
On 24 September 1861, Crown Princess Victoria introduced her brother Albert Edward to Alexandra at Speyer, but it was not until almost a year later on 9 September 1862 (after his affair with Nellie Clifden and the death of his father) that Albert Edward proposed to Alexandra at the Royal Castle of Laeken, the home of his great-uncle, King Leopold I of Belgium.
A few months later, Alexandra travelled from Denmark to Britain aboard the royal yacht Victoria and Albert II and arrived in Gravesend, Kent, on 7 March 1863.
The couple were married on 10 March 1863 at St George's Chapel, Windsor Castle, by Thomas Longley, the Archbishop of Canterbury.
Alexandra's first child, Albert Victor, was born two months premature in early 1864. Alexandra was devoted to her children: "She was in her glory when she could run up to the nursery, put on a flannel apron, wash the children herself and see them asleep in their little beds." Albert Edward and Alexandra had six children in total: Albert Victor, George, Louise, Victoria, Maud and John. All of Alexandra's children were apparently born prematurely.
With the death of her mother-in-law, Queen Victoria, in 1901, Alexandra became queen-empress consort to the new king.